Laser-welded article

ABSTRACT

A laser-welded article comprises: an integral construction of piled workpieces, that are welded by exothermic through irradiating laser and include thermoplastic resin, comprises of a laser-transmissible-absorptive molded workpiece including a thermoplastic resin and 0.001 to 0.3 weight % of colorant consisting of nigrosine which has an absorption coefficient: ε for a ray of 940 nm ranging form 4000 to 7000, that transmits laser partially and absorbs laser partially, and a laser-absorptive molded workpiece including a thermoplastic resin and 0.1 to 5 weight % of diverse colorant comprising of nigrosine and/or carbon black, that absorbs the laser.

BACKGROUND OF THE INVENTION

This invention relates to a laser-welded article that alaser-transmissible-absorptive molded workpiece including nigrosinealone as colorant and a laser-absorptive molded workpiece are welded bylaser at a time and unified.

For mutually joining workpieces made from a synthetic thermoplasticresin material, a method for laser welding is known.

Such laser welding is executed for example as follows. As shown in FIG.2, a laser-transmissible workpiece 11 is used for one workpiece and forthe other workpiece, a laser-absorptive workpiece 12 is used. Theseworkpieces are then put together. A laser 13 is irradiated from a sideof the laser-transmissible workpiece 11 towards the laser-absorptiveworkpiece 12. And the laser 13 transmitted through thelaser-transmissible workpiece 11 is absorbed into the laser-absorptiveworkpiece 12, and then exothermic is caused thereat. The exothermicmelts the laser-absorptive workpiece 12 mainly at a laser-absorbingpart, and then it melts the laser-transmissible workpiece 11 to weldboth workpieces. After cooling, the laser-transmissible workpiece 11 andthe laser-absorptive workpiece 12 are firmly joined at a weldingposition 14.

Merits of the laser welding are feasibility of welding workpieceswithout any contacts of a laser beam source to workpieces being due toweld; little thermal influence on laser-absorbing neighborhood by localexothermic; no threat of mechanical vibration; feasibility of mutuallywelding fine parts or workpieces having three-dimensionally complicatedstructures; excellent reproducibility; feasibility of maintainingsufficient airtightness; excellent welding strength; difficulty ofrecognizing a boundary line of a welding position by visual observation;no generation of dust and so on.

According to the laser welding, it is not only capable of weldingcertainly by simple operation but also achieving equal or more weldingstrength, as compared with prior methods for joining resin parts.Examples of the prior methods for joining resin parts are clamping by aclamp such as a bolt, a screw, a clip and so on, adhering by an adhesivematerial, vibration welding, ultrasonic welding and so on. The laserwelding also achieves labor saving, improvement of productivity,lowering of production costs and so on because of its little vibratoryor thermal influence on the laser-welded article. Accordingly, under anautomobile industry, electric industry or electronic industry forexample, the laser welding is practical for joining functional parts orelectronic parts that are due to avoid the vibratory or thermalinfluence thereon. Also the laser welding can be adapted for joiningresin parts having a complicated shape.

In Japanese Patent Provisional Publication No. 2004-148800, a method forthe laser welding is mentioned. In the method, a first resin workpiecethat has weak absorptiveness to a laser and a second resin workpiecethat is absorptive to a laser are put together, and then a laser isirradiated from a side of the first resin workpiece to weld bothworkpieces. In this case, however, the first resin workpiece is preparedby kneading a resin and an additive such as a copolymer of ethyleneand/or propylene and another olefin or vinyl compound. And the firstresin workpiece includes relatively much additive. Therefore, there is aproblem that the resin property of the first resin workpiece is easilyinfluenced by the additive. Also, there are some other problems.Depending on a sort of the resin and the additive, a separation oflayers in the kneading procedure, a deterioration of strength of thewelded article, and a restriction of using any resin are caused.

SUMMARY OF THE INVENTION

The present invention has been developed to solve the foregoingproblems. It is an object of the present invention to provide alaser-welded article that workpieces prepared simply can be easilyunified by laser in one laser welding process without using complicatedprocesses. Moreover, the laser-welded article has sufficient weldingstrength and excellent appearance, and does not damage the resinproperty.

A laser-welded article of the present invention developed foraccomplishing the foregoing objects comprises: an integral constructionof piled workpieces, that are welded by exothermic through irradiatinglaser, comprises of

-   a laser-transmissible-absorptive molded workpiece including a    thermoplastic resin and 0.001 to 0.3 weight % of colorant consisting    of nigrosine which has an absorption coefficient: ε for a ray of 940    nm ranging form 4000 to 7000 (ml/g·cm), that transmits laser    partially and absorbs laser partially,-   and a laser-absorptive molded workpiece including a thermoplastic    resin and 0.1 to 5 weight % of diverse colorant comprising of    nigrosine and/or carbon black, that absorbs the laser.

That is to say, the laser-transmissible-absorptive molded workpiece is amolded workpiece that has a property of laser-transmissivity and also aproperty of weak laser-absorbancy.

The diverse colorant may include carbon black.

The diverse colorant may include furthermore nigrosine.

In the laser-welded article, the laser-transmissible-absorptive moldedworkpiece satisfies the following numerical expression(I)0.07≦a₁=ε₁C₁L₁≦0.8  (I)[in the numerical expression(I), a₁ is absorbance thereof, ε₁ (1/cm) isan absorption coefficient thereof, C₁ (weight %) is concentration of thecolorant therein, L₁, (cm) is thickness thereof].

In the laser-welded article, the laser-absorptive molded workpiecesatisfies the following numerical expression(II)1≦a₂=ε₂C₂L₂≦50  (II)[in the numerical expression(II), a₂ is absorbance thereof, ε₂ (1/cm) isan absorption coefficient thereof, C₂ (weight %) is concentration of thediverse colorant therein, L₂ (cm) is thickness thereof].

In the laser-welded article, nigrosine includes at least one selectedfrom a group consisting of compounds represented by the followingchemical formulas (1) to (4).

The laser-transmissible-absorptive molded workpiece includes at leastone thermoplastic resin selected from a group consisting of polyamideresin, polycarbonate resin, polyphenylene sulfide resin, polyesterresin, and polyolefin-type resin.

The laser-transmissible-absorptive molded workpiece includes the resinof polyamide resin and 0.01 to 0.2 weight % of the colorant consistingof nigrosine.

The laser-transmissible-absorptive molded workpiece includes the resinof polycarbonate resin and 0.01 to 0.2 weight % of the colorantconsisting of nigrosine.

Concentration of iron in nigrosine is 1% at maximum.

Concentration of aniline in nigrosine is 1% at maximum.

The laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece have thickness ranging from 200 to5000 microns.

The laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece are films having thickness rangingfrom 200 to 1000 microns.

The laser-welded article of the present invention keeps the best ofintrinsic properties of the resin used for the molded workpiece becausea trace of nigrosine in the laser-transmissible-absorptive moldedworkpiece of the laser-welded article has sufficient solubility intooil, compatibility for the resin, solubility for the resin and aretardation effect.

Especially the laser-welded article using thelaser-transmissible-absorptive molded workpiece is firmly welded becausethe laser properly causes the exothermic for melting widely to weld.Therefore, the laser-welded article having sufficient tensile stressstrength and welding strength is obtained.

The laser-welded article is simply manufactured without requiring anyinconvenient pretreatments for adhering workpieces made from resin orcomplicated processes such as alloying. This laser-welded article iswelded by laser in one laser welding process and therefore has highproductive efficiency.

And adhesive materials or clamps for joining are not used for thelaser-welded article. Therefore, the laser-welded article has excellentrecycling property.

BRIEF EXPLANATION OF THE DRAWINGS

FIG. 1 shows one embodiment of a laser-welded article to which thepresent invention is applied.

FIG. 2 shows one embodiment of a laser-welded article to which thepresent invention is not applied.

DETAILED DESCRIPTION OF THE INVENTION

Hereunder one embodiment of the laser-welded article of the presentinvention is explained in detail as referring to FIG. 1 that correspondsto Examples.

A laser-transmissible-absorptive molded plate workpiece 1 that includescolorant consisting of nigrosine, and a laser-absorptive moldedworkpiece 2 that includes diverse colorant consisting of nigrosineand/or carbon black are employed for a laser-welded article. Theworkpieces are put together to pile at an end part thereof and arefirmly welded and unified to prepare a laser-welded article that is anintegral construction of the workpieces.

Incidentally the laser-transmissible-absorptive molded workpiece 1 andthe laser-absorptive molded workpiece 2 are allowed to take an optionalshape. The workpieces may be respectively plural components of flatfilms or plates having even thickness, as mentioned above. Theworkpieces may be respectively plural components of curved or bendedplates or boxes. And as shown in FIG. 2, the workpieces may respectivelyhave a stair of a joint flap at the put position.

One embodiment of the manufacturing process for the laser-welded articleis explained in detail. The manufacturing process thereof consists ofthe following procedures (A) to (F), for example.

-   (A) A resin and 0.001 to 0.3 weight % of colorant consisting of    nigrosine which has an absorption coefficient: ε for a ray of 940 nm    ranging from 4000 to 7000 (ml/g·cm) are kneaded and molded to    prepare a laser-transmissible-absorptive molded workpiece 1. In    order to transmit suitable quantity of partial laser for laser    welding and to absorb suitable quantity of residual laser, the    workpiece 1 is controlled by increasing or decreasing the amount of    colorant.-   (B) A resin and 0.1 to 5 weight % of the diverse colorant consisting    of carbon black and/or nigrosine that is much than the same or    different nigrosine in the laser-transmissible-absorptive molded    workpiece 1, are kneaded and molded to prepare a laser-absorptive    molded workpiece 2. In order to absorb the laser for laser welding,    the laser-absorptive molded workpiece 2 is controlled by increasing    or decreasing the amount or composition of diverse colorant.-   (C) The laser-transmissible-absorptive molded workpiece 1 and the    laser-absorptive molded workpiece 2 are put together. If necessary    on the occasion of putting the molded workpieces 1 and 2 for fixing,    they may be put together by pressing with a holding tool. And a    material having antireflection property such as an antireflection    film, another material having cooling effect, or a gas treatment    equipment may be placed at a side of the    laser-transmissible-absorptive molded workpiece.-   (D) Output power of a laser 3 is regulated properly in order that a    suitable quantity of the laser 3 transmits through the    laser-transmissible-absorptive molded workpiece 1 and also that a    suitable quantity of the residual laser is absorbed into the    laser-absorptive molded workpiece 2. The regulated laser 3 having    proper output power is irradiated from a side of the    laser-transmissible-absorptive molded workpiece 1.-   (E) The partial laser 3 transmits through the    laser-transmissible-absorptive molded workpiece 1, and the other    partial laser 3 is absorbed into the molded workpiece 1 and then    causes exothermic. The laser 3 transmitted through the    laser-transmissible-absorptive molded workpiece 1 reaches and is    absorbed into the laser-absorptive molded workpiece 2 and then    causes exothermic. Mainly at these exothermic parts, the    laser-transmissible-absorptive molded workpiece 1 and the    laser-absorptive molded workpiece 2 melt.-   (F) When the melting position thereof is cooled down and then    hardens, the laser-transmissible-absorptive molded workpiece 1 and    the laser-absorptive molded workpiece 2 are welded. Consequently,    the workpieces 1 and 2 are firmly joined at a welding position 4 and    are unified to become a laser-welded article of an integral    construction.

According to a prior method for a laser welding to prepare alaser-welded article made of the laser-transmissible molded workpieceand the laser-absorptive molded workpiece, an exothermic caused byirradiating laser to the laser-absorptive workpiece entirely melts thelaser-absorptive molded workpiece. The exothermic then melts thelaser-transmissible molded workpiece. Therefore, thermal efficiencythereof is not so superior. The resin of the laser-absorptive moldedworkpiece melts largely, but the resin of the laser-transmissible moldedworkpiece melts slightly. Therefore, the welding strength thereof isinsufficient.

On the other hand, the laser-welded article of the present invention ismade of the laser-transmissible-absorptive molded workpiece 1 includingcolorant consisting of nigrosine and the laser-absorptive moldedworkpiece 2, and both workpieces 1 and 2 cause exothermic. Therefore,temperature gradient between both workpiece 1 and 2 is negligible. And,the laser welding is efficiently performed using lower output power.Furthermore, melted resin positions of both workpieces 1 and 2 arelarger. Consequently, the welding strength thereof is extremelysufficient.

Examples of laser used for the laser welding are solid laser such as Nd:yttrium aluminum garnet (YAG) excitation and semiconductor laserexcitation, semiconductor laser, tunable diode laser, titanium-sapphirelaser (Nd : YAG excitation) and so on. Other examples are a halogen lampand a xenon lamp that generates infrared rays having wavelength of 700nm or more. Among these lasers, the irradiated laser ranging from 800 nmto 1600 nm that is a longer wavelength compared with visible radiationis usually used for the laser welding. The irradiated laser ispreferably ranging from 800 nm to 1100 nm.

The infrared rays or the laser is allowed to be irradiated vertically orslantingly towards a surface of the laser-transmissible-absorptivemolded workpiece. The laser is allowed to be irradiated from sole orplural direction.

The output power of the laser is regulated properly according toscanning speed and laser-absorptivity of thelaser-transmissible-absorptive molded workpiece and laser-absorptivemolded workpiece. If the output power is too insufficient, the resins ofthe workpieces are hard to melt at put surfaces thereof mutually. If theoutput power is excess, the resins of the workpieces vaporize ordeteriorate, and the welding strength thereof is insufficient. Foradapting the irradiation conditions, width or time of irradiating theinfrared rays or the laser is regulated properly.

The laser-welded article unified by these procedures develops thepractically sufficient welding strength at the welding positions. Alsowhen the laser-welded article is welded under proper conditions, thetensile stress strength thereof in accordance with Japanese IndustrialStandard K-7113-1995 is 300N or more.

When the laser-welded article is used for a medical tube of infusion ofinstillation, for a spout pouch of fluid diet or beverage compositionand so on, it must be safely used without leaking. For that purpose, itis preferable that the laser-welded article has the thickness of 200 to5000 microns of the laser-transmissible-absorptive molded workpiece. Ifthe thickness of the laser-transmissible-absorptive molded workpiece isless than 200 microns, it is difficult to control the laser energy.Therefore, the melting by the exothermic in the laser welding process isinsufficient or excess. As a result, the laser-welded article is brokenby overheating or cannot achieve sufficient welding strength. On theother hand, if the thickness of the laser-transmissible-absorptivemolded workpiece is more than 5000 microns, the transmissivity for thelaser decreases. As a result, the laser-welded article cannot achievesufficient welding strength.

Especially it is preferable that the laser-transmissible-absorptivemolded workpiece is composed of films having the thickness of 200 to1000 microns.

The laser-transmissible-absorptive molded workpiece is explainedconcretely.

A mixture of nigrosine and a resin such as a laser-transmissible resinis molded to prepare the laser-transmissible-absorptive moldedworkpiece. The laser-transmissible-absorptive molded workpiece hasproperties of transmitting quantity of partial laser and absorbingquantity of residual laser. The properties are proceeded from a littleamount of the colorant consisting of nigrosine in the molded workpiece.The colorant absorbs the quantity of partial laser with resonancetowards wavelength of the laser and transmits the quantity of residuallaser.

Examples of the laser-transmissible resin are a resin havinglaser-transmissible property used as a dispersant for the pigment, andknown resin used as carrier resin of masterbatch or colored pellets.Concrete typical examples of the resin are thermoplastic resins such aspolyphenylene sulfide resin; polyamide resin (PA); polyethylene resin;polypropylene resin; polystyrene resin; polymethylpentene resin;methacrylate resin; acrylpolyamide resin; ethylenevinylalcohol (EVOH)resin; polycarbonate resin (PC); polyester resin illustrated withpolyethylene terephthalate (PET), polybutylene terephthalate (PBT) andso on; polyacetal resin; polyvinyl chloride resin; polyvinylidenechloride resin; polyphenylene oxide resin; polyarylate resin;polyallylsulfone resin; fluorine-contained resin; liquid crystal polymerand so on.

Further, the thermoplastic resin is allowed to be a copolymer resin madefrom two or more monomers and so on that construct the above-mentionedthermoplastic resins. Concrete examples of the copolymer resin areacrylonitrile-styrene copolymer resin (AS),acrylonitrile-butadiene-styrene copolymer resin (ABS),acrylonitrile-ethylene propylene diene monomer-styrene copolymer resin(AES), polyamide-polybutylene terephthalate copolymer resin (PA-PBT),polyethylene terephthalate-polybutylene terephthalate copolymer resin(PET-PBT), polycarbonate-polybutylene terephthalate copolymer resin(PC-PBT), polycarbonate-polyamide copolymer resin (PC-PA) and so on. Andother concrete examples of the resin are a thermoplastic elastomer suchas polystyrene-type thermoplastic elastomer, polyolefin-typethermoplastic elastomer, polyurethane-type thermoplastic elastomer, andpolyester-type thermoplastic elastomer; synthetic wax or natural waxthat contains the above-mentioned resins as the main component.Incidentally, molecular weight of the thermoplastic resins is notintended to be limited. Also, the thermoplastic resins may be usedsolely or plurally.

It is preferable that the thermoplastic resin is polyamide resin (Nylonthat is a registered trademark), polycarbonate resin, polyphenylenesulfide resin (PPS), polyester resin of which PET and PBT belong to thecategory, and polyolefin-type resin of which polypropylene (PP) andpolyethylene (PE) belong to the category. It is further preferable thatthe thermoplastic resin is polyamide resin, polycarbonate resin orpolyolefin-type resin, taking transmittance into consideration. It isfurthermore preferable that the thermoplastic resin is the polyamideresin (Nylon).

Examples of the polyamide resin (Nylon) are nylon 6, nylon 66, nylon 46,nylon 11, nylon 12, nylon 69, nylon 610, nylon 612, nylon 96,non-crystal nylon, nylon having high melting point, nylon RIM, nylonMIX6 and so on; copolymer of two or more kinds thereof such as nylon6/66 copolymer, nylon 6/66/610 copolymer, nylon 6/66/11/12 copolymer,crystal nylon/non-crystal nylon copolymer and so on. The polyamide resinmay be mixed polymer of polyamide resin and another synthetic resin.Examples of the mixed polymer are polyamide/polyester mixed polymer,polyamide/polyphenyleneoxide mixed polymer, polyamide/polycarbonatemixed polymer, polyamide/polyolefin mixed polymer,polyamide/styrene/acrylonitrile mixed polymer, polyamide/polyacrylatemixed polymer, polyamide/silicone mixed polymer and so on. Thesepolyamide resins may be used solely or plurally.

Polycarbonate is a thermoplastic resin having bindings of carbonic esterin principle chain thereof. Polycarbonate has a mechanical property forstrength, heat resistance, cold resistance, electrical property,transparency and so on and is a typical engineering plastic.Polycarbonate that is industrially manufactured at present is aromaticpolycarbonate made from bisphenol A. Examples of method formanufacturing thereof are a method using phosgene and a method by esterinterchange. The molecule thereof has a liner chemical structure thatmany carbonic ester groups having aromatic hydrocarbon group are bound.The chemical structure has bulky benzene rings and flexible carbonicester groups in the principle chain. The bulky benzene rings accomplishhigh temperature for thermal deforming and excellent physical ormechanical properties. The flexible carbonic ester groups contribute tomoldability and flexibility, however easily cause hydrolysis.

The colorant included in a laser-transmissible-absorptive moldedworkpiece consists of nigrosine that has an absorption coefficient (i.e.absorbency index): ε for a ray of 940 nm ranging form 4000 to 7000(ml/g·cm). If the absorption coefficient: ε thereof exceeds 7000,transmittance of the irradiated laser is so low that the weldingstrength of the laser-welded article is insufficient. If the absorptioncoefficient: ε thereof is less than 4000, the exothermic is so littlethat the welding strength of the laser-welded article is insufficient.

A method for determining the absorption coefficient (i.e. absorbencyindex): ε is as follows. 0.05 g of laser-transmissible absorbent areexactly weighed and dissolved in solvent for exampleN,N-dimethylformamide (DMF) by using 50 ml of a volumetric flask. Then 1ml thereof is diluted by DMF to prepare a measuring sample. Foremost anabsorbance to rays of 940 nm is determined by using a spectrophotometerUV1600PC, which is available from Shimadzu Corporation. Then anabsorption coefficient (i.e. absorbency index): ε (ml/g·cm) iscalculated using the absorbance.

Examples of nigrosine are a black azine-type condensed mixture such asC. I. SOLVENT BLACK 5 and C. I. SOLVENT BLACK 7 described on COLORINDEX. It is preferably C. I. SOLVENT BLACK 7. The nigrosines aresynthesized by reaction of oxidation and dehydrating condensation ofaniline, aniline hydrochloride and nitrobenzene at 160° C. to 180° C. asreaction temperature under the existence of iron chloride. NUBIAN BLACKseries as the nigrosine is commercially available from Orient ChemicalIndustries, Ltd.,

An average particle size of nigrosine as color is preferably rangingfrom 5 to 20 microns, and it is furthermore preferably ranging from 5 to15 microns. When the above nigrosine as color is used, a weldingprocedure is easily performed and the even laser-welded article isprepared.

Concentration of iron in nigrosine is for example less than 1 weight %,preferably less than 0.5 weight %, furthermore preferably less than 0.4weight %. This improves dispersibility or compatibility of nigrosin ascolor for the resin and therefore the quality laser-welded article madefrom the resin is prepared. Content of iron in nigrosine is determinedby atomic absorption spectrometry. An example of a decreasing treatmentfor iron is a following procedure. Aniline or aniline hydrochloride withnitrobenzene under presence of ferric chloride is condensed to preparenigrosine condensation product. Sodium hydroxide is added to thecondensation product to treat into base for nigrosine. Ferric hydroxideis obtained as iron component. Obtained ferric hydroxide is removed by acentrifugal separator such as screw-decanter-type, sharpless-type and soon. After drying, iron content in nigrosine is decreased and adapted.

Concentration of aniline in nigrosine is for example less than 1 weight%, preferably less than 0.5 weight %, furthermore preferably 0.4 weight%. Examples of a decreasing treatment for aniline are followingprocedures.

-   (i) A procedure comprises of adding solvent having a boiling point    ranging from 100 to 230° C., and then heating and reducing pressure    to remove aniline or nitrobenzene with the solvent. (Incidentally,    examples of the solvent are xylene, toluene, ethylbenzene,    mesitylene, decahydronaphthalene, dibutyl ether, ethylene glycol and    so on.)-   (ii) A procedure comprises of removing nigrosine by washing with    solution that has capacity for dissolving aniline. (Incidentally,    examples of the solution are organic solvent such as alcohol,    aqueous solution, mixed solution of organic solvent and water, or    acidic solution thereof.)-   (iii) A procedure comprises of a removing procedure by heating and    reducing pressure merely.-   (iv) A procedure comprises of a heating and evaporating procedure.-   (v) A procedure comprises of a distilling procedure such as steam    distillation and so on.-   (vi) A procedure comprises of oxidation procedure using oxygen,    ozone or various oxidant.

When nigrosine includes at least one selected from a group consisting ofcompounds represented by the before-mentioned chemical formulas (1) to(4), the laser-welded article having pretty appearance and sufficientwelding strength is obtained advantageously.

And Content of nigrosine to the laser-transmissible resin is preferably0.001 to 0.3 weight %. If the content is less than 0.001 weight %, theexothermic through absorption of energy of the laser is so insufficientthat the exothermic fails to raise the temperature and the weldingstrength at the welded position of the laser-transmissible-absorptivemolded workpiece and the laser-absorptive molded workpiece isinsufficient. If the content excesses 0.3 weight %, thelaser-transmittance is easy to decrease and the welding strength betweenthe mutual workpieces is insufficient.

When the laser-transmissible resin is polyamide resin, the content ofnigrosine is preferably ranging from 0.01 to 0.2 weight %. When thelaser-transmissible resin is polycarbonate resin, the content ofnigrosine is preferably ranging from 0.01 to 0.2 weight %. It is becausethe exothermic is properly generated and the sufficient welding strengthbetween the mutual workpieces is accomplished.

The absorbance a₁ of the laser-transmissible-absorptive molded workpieceis adjusted to satisfy the following numerical expression (1).0.07≦a₁=ε₁C₁L₁≦0.8  (I)[in the numerical expression(I), a₁ is absorbance thereof, ε₁ (1/cm) isabsorption coefficient thereof, C₁ (weight %) is concentration of thecolorant therein, L₁ (cm) is thickness thereof].

In this occasion, If the absorbance: a₁ is less than 0.07, theexothermic through absorption of energy of the laser into thelaser-transmissible-absorptive molded workpiece is so insufficient thatthe exothermic fails to raise the temperature and the welding strengthat the welded position of the laser-transmissible-absorptive moldedworkpiece and the laser-absorptive molded workpiece is insufficient. Ifthe absorbance: a₁ excesses 0.8, the laser-transmittance of thelaser-transmissible-absorptive molded workpiece decreases, and thewelding strength between the laser-transmissible-absorptive moldedworkpiece and the laser-absorptive molded workpiece is insufficient.

It is preferable that the laser-transmissivity T₁ (%) of thelaser-transmissible-absorptive molded workpiece to the laser of 940 nmis ranging from 14% to 80%. This laser-transmissivity T₁ to the laser isa value measured from a molded plate of 1 mm thickness of thelaser-transmissible-absorptive molded workpiece.

For preparing the laser-transmissible-absorptive molded workpiece, thelaser-transmissible resin may include various additives if necessary.Examples of the additive are an auxiliary coloring agent, a dispersant,a reinforcer (or a filler), a stabilizer, a plasticizer, a reformingagent, an ultraviolet-absorptive agent (or a light-stabilizer), anantioxidant, an antistatic agent, a lubricant, a mold releasing agent, acrystallization accelerator, a crystalline germ agent, a flame retarderand so on.

The reinforcer, which is used for general reinforcement of a syntheticresin, is not intended to be limited. Examples of the reinforcer are aglass fiber, a carbon fiber, other inorganic fibers, and other organicfibers made from aramid, polyphenylene sulfide resin (PPS), nylon,polyester, liquid crystal polymer and so on. The glass fiber ispreferable for the reinforcement of the resin, which is required atransparent. In order to practically use the glass fiber, it ispreferable that the length of the glass fiber is ranging from 2 to 15 mmand the diameter thereof is ranging from 1 to 20 microns. A shape of theglass fiber is not intended to be limited. Examples of the shape thereofare a roving, a milled fiber and so on. The glass fiber can be usedsolely or plurally.

Examples of the filler are a plate-shaped filler such as mica, sericiteand glass flakes; silicate such as talc, kaolin, clay, wollastonite,bentonite, asbestos and alumina silicate; metal oxide such as alumina,silicon oxide, magnesium oxide, zirconium oxide and titanium oxide;carbonate such as calcium carbonate, magnesium carbonate and dolomite;sulfate such as calcium sulfate and barium sulfate; granular filler suchas glass beads, ceramic beads, boron nitride and silicon carbide.

The laser-transmissible-absorptive molded workpiece may be prepared byusing a masterbatch of the laser-transmissible-absorptive coloredthermoplastic resin composition. The masterbatch may be prepared by anarbitrary method. For example, the masterbatch may be prepared by mixinga resin powder or pellets as the base of the masterbatch and thecolorant with a mixer such as a tumbler, a supermixer and so on, heatingand melting the mixture with a extruder, a batch-type kneader or aroll-type kneader and so on, and then forming pellets or grain.

Molding process of the laser-transmissible-absorptive molded workpiecemay be executed by general various procedures. For example, the moldingprocess may be executed by using the colored pellets with a processingmachine such as an extruder, an injection molding machine, a roll milland so on. Another molding process may be executed with the proper mixerby mixing the pellets or the grain made from a transparent resin, agranulated colorant, and if necessary, various additives, and then themixture is molded with a processing machine. Another molding process maybe executed by adding the colorant to a monomer including a properpolymerization catalyst, polymerizing the mixture to obtain the desiredresin, and then molding the obtained resin by a proper procedure.Examples of the molding procedure may be general molding procedures suchas injection molding, extrusion molding, compression molding, foamingmolding, blow molding, vacuum molding, injection blow molding,rotational molding, calendaring molding, solution casting and so on. Thelaser-transmissible-absorptive molded workpieces having various shapesare obtained by these molding procedures.

The laser-absorptive molded workpiece is explained concretely.

The mixture of a laser-transmissible resin, which is the same as theresin of the before-mentioned laser-transmissible-absorptive moldedworkpiece, and a colorant that is dispersed in the resin and absorbs thelaser are molded to prepare the laser-absorptive molded workpiece. Whenthe laser is irradiated thereto, the laser is absorbed and thelaser-absorptive molded workpiece melts.

According to uses or purposes, the laser-transmissible resin mayproperly include various additives such as the same type of additives asmentioned before. Examples of the additives are an auxiliary coloringagent, a dispersant, a reinforcer (or a filler), a stabilizer, aplasticizer, a reforming agent, an ultraviolet-absorptive agent (or alight-stabilizer), an antioxidant, an antistatic agent, a lubricant, amold releasing agent, a crystallization accelerator, a crystalline germagent, a flame retarder and so on.

Examples of the colorant in the laser-absorptive molded workpiece thatabsorbs the laser are carbon black and/or nigrosine. The colorant meansnigrosine, carbon black, or mixture of nigrosine and carbon black. Andhereunder it is often expressed with the colorant that absorbs thelaser. The colorant that causes the exothermic by absorption of thelaser much to energy density is carbon black, or combination of carbonblack and nigrosine. An amount of nigrosine is regulate as to an amountof carbon black according to the condition of the laser welding, and theexothermic quantity of the laser-absorptive molded workpiece iscontrolled properly.

The laser-absorptive molded workpiece includes 0.1 to 5 weight %,preferably 0.1 to 2 weight %, of the diverse colorant comprising ofnigrosine and/or carbon black.

The proper amount of the diverse colorant is mentioned according tokinds thereof.

When the colorant in the thermoplastic resin that absorbs the laserconsists of carbon black, the amount of the colorant is 0.1 to 0.3weight %. When the colorant in the thermoplastic resin that absorbs thelaser consists of nigrosine, the amount thereof is 0.1 to 0.7 weight %.When the colorant consists of combination of carbon black and nigrosine,the amount thereof is 0.1 to 0.6 weight %. A rate of the combination ofcarbon black and nigrosine is preferably 1:2 to 2:1.

The transmissivity of the laser-absorptive molded workpiece to theirradiated laser is preferablly 5% or less. If the transmissivityexcesses 5%, the energy of laser that transmits thelaser-transmissible-absorptive molded workpiece and then is absorbedinto the laser-absorptive molded workpiece is insufficient or is lost.

The absorbance a₂ of the laser-absorptive molded workpiece is adjustedto satisfy the condition of the following numerical expression (11).1≦a₂=ε₂C₂L₂≦50  (II)(In the numerical expression (II), ε₂ (1/cm) is an absorptioncoefficient thereof, C₂ (weight %) is concentration of the laserabsorbent that absorbs the laser, L₂ (cm) is the thickness thereof).

In this occasion, if the absorbance a₂ is less than 1, the exothermiccaused by the laser-absorptive molded workpiece absorbing energy of thelaser is weak. Therefore, the temperature is not sufficiently increased,and thus the sufficient welding strength between thelaser-transmissible-absorptive molded workpiece and the laser-absorptivemolded workpiece cannot be achieved. On the other hand, if theabsorbance a₂ is more than 50, the exothermic of the laser-absorptivemolded workpiece absorbing laser energy becomes excess. Therefore, thevoids generate, or the welding strength between thelaser-transmissible-absorptive molded workpiece and the laser-absorptivemolded workpiece decreases.

When the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece of the laser-welded article are allcolored with the same color, the appearance between the welded moldedworkpieces colored the same does not show any difference in color.Therefore, the appearance thereof looks pretty.

For preparing the laser-absorptive molded workpiece, the same materialsas described for preparing the laser-transmissible-absorptive moldedworkpiece can be used except for including the colorant that isabsorptive to the laser. Also according to uses and purposes, variousadditives may be properly included.

Following examples describe embodiments concretely. The presentinvention is not intended to be limited to specific embodiments.

The laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were manufactured experimentally, andthen they were welded by the laser.

Examples of experimentally manufacturing the laser-welded articles towhich the present invention was applied are shown in Examples 1 to 6.Examples of the laser-welded articles to which the present invention wasnot applied are shown in Comparative Examples 1 to 4.

EXAMPLE 1

(1-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

499.9 g of a fiber-reinforced polyamide 6 resin of catalog No. ZYTEL73G30L available from Du Pont that ZYTEL is a registered trademark and0.1 g of nigrosine of catalog No. NUBIAN BLACK PA9801 available fromOrient Chemical Industries, Ltd., which contains 0.75% of iron and 1.08%of aniline, and NUBIAN is a registered trademark, were added in atumbler made of stainless steel and were mixed with stirring for 1 hour.The obtained mixture was molded at 280° C. of temperature of a cylinderand 80° C. of temperature of a metal mold with general procedures usingan injection molding machine of catalog No. Si-50, which is availablefrom Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(1-b) Preparation of Laser-Absorptive Molded Workpiece

499 g of the fiber-reinforced polyamide 6 resin of catalog No. ZYTEL73G30L available from Du Pont that ZYTEL is the registered trademark and1.0 g of carbon black of catalog No. #32 available from MitsubishiChemical Corporation were added in a tumbler made of stainless steel andwere mixed with stirring for 1. The obtained mixture was molded at 280°C. of temperature of a cylinder and 80° C. of temperature of a metalmold with general procedures using the injection molding machine ofcatalog No. Si-50, which is available from Toyo Machinery & Metal Co.,Ltd. Then a laser-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(1-c) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 10 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 2 mm/sec. of scanning speed for 20 mm toobtain a laser-welded article.

Incidentally the absorption coefficient: ε of nigrosine of NUBIAN (theregistered trademark) BLACK PA9801 to rays of 940 nm in DMF was 6.0×10³(ml/g·cm).

EXAMPLE 2

(2-a) Preparation of Laser-Transmissible-Absorptive Molded workpiece

499.65 g of the fiber-reinforced polyamide 6 resin of catalog No. ZYTEL73G30L available from Du Pont that ZYTEL is the registered trademark and0.35 g of nigrosine of catalog No. NUBIAN BLACK PA9801 available fromOrient Chemical Industries, Ltd that NUBIAN is the registered trademarkwere added in a tumbler made of stainless steel and were mixed withstirring for 1 hour. The obtained mixture was molded at 280° C. oftemperature of a cylinder and 80° C. of temperature of a metal mold withgeneral procedures using the injection molding machine of catalog No.Si-50, which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(2-b) Preparation of Laser-Absorptive Molded Workpiece

A laser-absorptive molded workpiece having the length of 80 mm, thewidth of 50 mm and the thickness of 1 mm was prepared by procedures assame as ones of (1-b) in Example 1.

(2-c) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 10 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 1mm/sec. of scanning speed for 20 mm toobtain a laser-welded article.

EXAMPLE 3

(3-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

499.65 g of the fiber-reinforced polyamide 6 resin of catalog No. ZYTEL73G30L available from Du Pont that ZYTEL is the registered trademark and0.35 g of nigrosine of catalog No. NUBIAN BLACK PA9803 available fromOrient Chemical Industries, Ltd., which contains 0.26% of iron and 0.15%of aniline, and NUBIAN is the registered trademark, were added in atumbler made of stainless steel and were mixed with stirring for 1 hour.The obtained mixture was molded at 280° C. of temperature of a cylinderand 80° C. of temperature of a metal mold with general procedures usingthe injection molding machine of catalog No. Si-50, which is availablefrom Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(3-b) Preparation of Laser-Absorptive Molded Workpiece

A laser-absorptive molded workpiece having the length of 80 mm, thewidth of 50 mm and the thickness of 1 mm was prepared by procedures assame as ones of (1-b) in Example 1.

(3-c) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(2-c) in Example 2.

Incidentally the absorption coefficient: ε of nigrosine of NUBIAN (theregistered trademark) BLACK PA9803 to rays of 940 nm in DMF was 6.4×10³(ml/g·cm).

EXAMPLE 4

(4-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

499.5 g of the fiber-reinforced polyamide 6 resin of catalog No. ZYTEL73G30L available from Du Pont that ZYTEL is the registered trademark and0.5 g of nigrosine of catalog No. NUBIAN BLACK PA9801 available fromOrient Chemical Industries, Ltd that NUBIAN is the registered trademarkwere added in a tumbler made of stainless steel and were mixed withstirring for 1 hour. The obtained mixture was molded at 280° C. oftemperature of a cylinder and 80° C. of temperature of a metal mold withgeneral procedures using the injection molding machine of catalog No.Si-50, which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(4-b) Preparation of Laser-Absorptive Molded Workpiece

A laser-absorptive molded workpiece having the length of 80 mm, thewidth of 50 mm and the thickness of 1 mm was prepared by procedures assame as ones of (1-b) in Example 1.

(4-c) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(2-c) in Example 2.

EXAMPLE 5

(5-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

499.8 g of Polyamide 66 resin of catalog No. ZYTEL 101NC available fromDu Pont that ZYTEL is the registered trademark and 0.2 g of nigrosine ofcatalog No. NUBIAN BLACK PA9801 available from Orient ChemicalIndustries, Ltd. that NUBIAN is the registered trademark were added in atumbler made of stainless steel and were mixed with stirring for 1 hour.The obtained mixture was molded at 270° C. of temperature of a cylinderand 60° C. of temperature of a metal mold with general procedures usingthe injection molding machine of catalog No. Si-50, which is availablefrom Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(5-b) Preparation of Laser-Absorptive Molded Workpiece

Polyamide 66 resin of catalog No. ZYTEL 101NC available from Du Pontthat ZYTEL is the registered trademark and nigrosine of catalog No.NUBIAN BLACK PA9801 available from Orient Chemical Industries, Ltd. thatNUBIAN is the registered trademark and carbon black of catalog No. #32available from Mitsubishi Chemical Corporation were added in a tumblermade of stainless steel and were mixed with stirring for 1 houraccording to composition rates shown in Table 1. The obtained mixturewas molded at 270° C. of temperature of a cylinder and 60° C. oftemperature of a metal mold with general procedures using the injectionmolding machine of catalog No. Si-50, which is available from ToyoMachinery & Metal Co., Ltd. Then a laser-absorptive molded workpiecehaving the length of 80 mm, the width of 50 mm and the thickness of 1 mmwas prepared.

(5-c) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 10 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 4 mm/sec. of scanning speed for 20 mm toobtain a laser-welded article.

EXAMPLE 6

(6-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

Nigrosine of catalog No. NUBIAN BLACK PA9803 available from OrientChemical Industries, Ltd. that NUBIAN is the registered trademark wasdried over using a paddle drier under reduced pressure at 250° C. for 12hours to prepare purified nigrosine which contains 0.20% of iron and0.07% of aniline. 499.65 g of the fiber-reinforced polyamide 6 resin ofcatalog No. ZYTEL 73G30L available from Du Pont that ZYTEL is theregistered trademark and 0.35 g of the purified nigrosine were added ina tumbler made of stainless steel and were mixed with stirring for 1hour. The obtained mixture was molded at 280° C. of temperature of acylinder and 80° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(6-b) Preparation of Laser-Absorptive Molded Workpiece

A laser-absorptive molded workpiece having the length of 80 mm, thewidth of 50 mm and the thickness of 1 mm was prepared by procedures assame as ones of (1-b) in Example 1.

(6-c) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(2-c) in Example 2.

Comparative Example 1

(1-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

500 g of the fiber-reinforced polyamide 6 resin of catalog No. ZYTEL73G30L available from Du Pont that ZYTEL is the registered trademark wasmolded at 280° C. of temperature of a cylinder and 80° C. of temperatureof a metal mold with general procedures using the injection moldingmachine of catalog No. Si-50, which is available from Toyo Machinery &Metal Co., Ltd. Then a laser-transmissible-absorptive molded workpiecehaving the length of 80 mm, the width of 50 mm and the thickness of 1 mmwas prepared.

(1-B) Preparation of Laser-Absorptive Molded Workpiece

The fiber-reinforced polyamide 6 resin of catalog No. ZYTEL 73G30Lavailable from Du Pont that ZYTEL is the registered trademark and carbonblack of catalog No. #32 available from Mitsubishi Chemical Corporationwere added in a tumbler made of stainless steel and were mixed withstirring for 1 hour according to composition rates as shown in Table 1.The obtained mixture was molded at 280° C. of temperature of a cylinderand 80° C. of temperature of a metal mold with general procedures usingthe injection molding machine of catalog No. Si-50, which is availablefrom Toyo Machinery & Metal Co., Ltd. Then a laser-absorptive moldedworkpiece having the length of 80 mm, the width of 50 mm and thethickness of 1 mm was prepared.

(1-C) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 10 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 2 mm/sec. of scanning speed for 20 mm toobtain a laser-welded article.

Comparative Example 2

(2-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

Polyamide 66 resin of catalog No. ZYTEL 101NC available from Du Pontthat ZYTEL is the registered trademark is used instead of thefiber-reinforced polyamide 6 resin of catalog No. ZYTEL 73G30L inComparative Example 1, which is available from Du Pont and that ZYTEL isthe registered trademark. Except for it and molding at 270° C. oftemperature of a cylinder and 60° C. of temperature of a metal mold, alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared byprocedures as same as ones of (1-A) in Comparative Example 1.

(2-B) Preparation of Laser-Absorptive Molded Workpiece

Polyamide 66 resin of catalog No. ZYTEL 101NC available from Du Pontthat ZYTEL is the registered trademark and carbon black of catalog No.#32 available from Mitsubishi Chemical Corporation were added in atumbler made of stainless steel and were mixed with stirring for 1 houraccording to composition rates shown in Table 1. The obtained mixturewas molded at 270° C. of temperature of a cylinder and 60° C. oftemperature of a metal mold with general procedures using the injectionmolding machine of catalog No. Si-50, which is available from ToyoMachinery & Metal Co., Ltd. Then a laser-absorptive molded workpiecehaving the length of 80 mm, the width of 50 mm and the thickness of 1 mmwas prepared.

(2-C) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 10 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 4 mm/sec. of scanning speed for 20 mm toobtain a laser-welded article.

Comparative Example 3

(3-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

The fiber-reinforced polyamide 6 resin of catalog No. ZYTEL 73G30Lavailable from Du Pont that ZYTEL is the registered trademark andnigrosine of catalog No. NUBIAN BLACK PA9801 available from OrientChemical Industries, Ltd. that NUBIAN is the registered trademark wereadded in a tumbler made of stainless steel and were mixed with stirringfor 1 hour according to composition rates shown in Table 1. The obtainedmixture was molded at 280° C. of temperature of a cylinder and 80° C. oftemperature of a metal mold with general procedures using the injectionmolding machine of catalog No. Si-50, which is available from ToyoMachinery & Metal Co., Ltd. Then a laser-transmissible-absorptive moldedworkpiece having the length of 80 mm, the width of 50 mm and thethickness of 1 mm was prepared.

(3-B) Preparation of Laser-Absorptive Molded Workpiece

A laser-absorptive molded workpiece having the length of 80 mm, thewidth of 50 mm and the thickness of 1 mm was prepared by procedures assame as ones of (1-B) in Comparative Example 1.

(3-C) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(1-C) in Comparative Example 1.

Comparative Example 4

(4-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

The fiber-reinforced polyamide 6 resin of catalog No. ZYTEL 73G30Lavailable from Du Pont that ZYTEL is the registered trademark andnigrosine of catalog No. NUBIAN BLACK PA9801 available from OrientChemical Industries, Ltd. that NUBIAN is the registered trademark wereadded in a tumbler made of stainless steel and were mixed with stirringfor 1 hour according to composition rates shown in Table 1. The obtainedmixture was molded at 280° C. of temperature of a cylinder and 80° C. oftemperature of a metal mold with general procedures using the injectionmolding machine of catalog No. Si-50, which is available from ToyoMachinery & Metal Co., Ltd. Then a laser-transmissible-absorptive moldedworkpiece having the length of 80 mm, the width of 50 mm and thethickness of 1 mm was prepared.

(4-B) Preparation of Laser-Absorptive Molded Workpiece

The fiber-reinforced polyamide 6 resin of catalog No. ZYTEL 73G30Lavailable from Du Pont that ZYTEL is the registered trademark andnigrosine of catalog No. NUBIAN BLACK PA9801 available from OrientChemical Industries, Ltd. that NUBIAN is the registered trademark wereadded in a tumbler made of stainless steel and were mixed with stirringfor 1 hour according to composition rates shown in Table 1. The obtainedmixture was molded at 280° C. of temperature of a cylinder and 80° C. oftemperature of a metal mold with general procedures using the injectionmolding machine of catalog No. Si-50, which is available from ToyoMachinery & Metal Co., Ltd. Then a laser-absorptive molded workpiecehaving the length of 80 mm, the width of 50 mm and the thickness of 1 mmwas prepared.

(4-C) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 10 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 1 mm/sec. of scanning speed for 20 mm toobtain a laser-welded article.

By using polycarbonate resin, the laser-transmissible-absorptive moldedworkpiece and the laser-absorptive molded workpiece were manufacturedexperimentally, and then they were welded by the laser. Examples ofexperimentally manufacturing the laser-welded articles to which thepresent invention was applied are shown in Examples 7 to 10. Examples ofthe laser-welded articles to which the present invention was not appliedare shown in Comparative Examples 5 to 7.

EXAMPLE 7

(7-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

499.9 g of the polycarbonate resin of catalog No. Panlite 1225Yavailable from TEIJIN Limited and 0.1 g of nigrosine of catalog No.NUBIAN BLACK PC0850 available from Orient Chemical Industries, Ltd.,which contains 0.1% of iron and 0.07% of aniline and that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour. The obtained mixture was molded at280° C. of temperature of a cylinder and 80° C. of temperature of ametal mold with general procedures using the injection molding machineof catalog No. Si-50, which is available from Toyo Machinery & MetalCo., Ltd. Then a laser-transmissible-absorptive molded workpiece havingthe length of 80 mm, the width of 50 mm and the thickness of 1 mm wasprepared.

(7-b) Preparation of Laser-Absorptive Molded Workpiece

495 g of the polycarbonate resin of catalog No. Panlite 1225Y availablefrom TEIJIN Limited and 5.0 g of nigrosine of catalog No. NUBIAN BLACKPC0850 available from Orient Chemical Industries, Ltd., and that NUBIANis the registered trademark were added in a tumbler made of stainlesssteel and were mixed with stirring for 1 hour. The obtained mixture wasmolded at 280° C. of temperature of a cylinder and 80° C. of temperatureof a metal mold with general procedures using the injection moldingmachine of catalog No. Si-50, which is available from Toyo Machinery &Metal Co., Ltd. Then a laser-absorptive molded workpiece having thelength of 80 mm, the width of 50 mm and the thickness of 1 mm wasprepared.

(7-c) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 8 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 2 mm/sec. of scanning speed for 20 mm toobtain a laser-welded article.

Incidentally the absorption coefficient: ε of nigrosine of NUBIAN (theregistered trademark) BLACK PC0850 to rays of 940 nm in DMF was 4.8×10³(ml/g·cm).

EXAMPLE 8

(8-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

The polycarbonate resin of catalog No. Panlite 1225Y available fromTEIJIN Limited and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour according to composition rates shownin Table 2. The obtained mixture was molded at 280° C. of temperature ofa cylinder and 80° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(8-b) Preparation of Laser-Absorptive Molded Workpiece

A laser-absorptive molded workpiece having the length of 80 mm, thewidth of 50 mm and the thickness of 1 mm was prepared by procedures assame as ones of (7-b) in Example 7.

(8-c) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(7-c) in Example 7.

EXAMPLE 9

(9-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

The polycarbonate resin of catalog No. Panlite 1225Y available fromTEIJIN Limited and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour according to composition rates shownin Table 2. The obtained mixture was molded at 280° C. of temperature ofa cylinder and 80° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(9-b) Preparation of Laser-Absorptive Molded Workpiece

A laser-absorptive molded workpiece having the length of 80 mm, thewidth of 50 mm and the thickness of 1 mm was prepared by procedures assame as ones of (7-b) in Example 7.

(9-c) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(7-c) in Example 7.

EXAMPLE 10

(10-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

The polycarbonate resin of catalog No. Panlite 1225Y available fromTEIJIN Limited and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour according to composition rates shownin Table 2. The obtained mixture was molded at 280° C. of temperature ofa cylinder and 80° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(10-b) Preparation of Laser-Absorptive Molded Workpiece

The polycarbonate resin of catalog No. Panlite 1225Y, available fromTEIJIN Limited and carbon black of catalog No. #32 available fromMitsubishi Chemical Corporation were added in a tumbler made ofstainless steel and were mixed with stirring for 1 hour according tocomposition rates shown in Table 2. The obtained mixture was molded at280° C. of temperature of a cylinder and 80° C. of temperature of ametal mold with general procedures using the injection molding machineof catalog No. Si-50, which is available from Toyo Machinery & MetalCo., Ltd. Then a laser-absorptive molded workpiece having the length of80 mm, the width of 50 mm and the thickness of 1 mm was prepared.

(10-c) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(7-c) in Example 7.

Comparative Example 5

(5-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

500 g of the polycarbonate resin of catalog No. Panlite 1225Y availablefrom TEIJIN Limited was molded at 280° C. of temperature of a cylinderand 80° C. of temperature of a metal mold with general procedures usingthe injection molding machine of catalog No. Si-50, which is availablefrom Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(5-B) Preparation of Laser-Absorptive Molded Workpiece

495 g of the polycarbonate resin of catalog No. Panlite 1225Y availablefrom TEIJIN Limited and 5.0 g of nigrosine of catalog No. NUBIAN BLACKPC0850 available from Orient Chemical Industries, Ltd., and that NUBIANis the registered trademark were added in a tumbler made of stainlesssteel and were mixed with stirring for 1 hour. The obtained mixture wasmolded at 280° C. of temperature of a cylinder and 80° C. of temperatureof a metal mold with general procedures using the injection moldingmachine of catalog No. Si-50, which is available from Toyo Machinery &Metal Co., Ltd. Then a laser-absorptive molded workpiece having thelength of 80 mm, the width of 50 mm and the thickness of 1 mm wasprepared.

(5-C) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 8 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 2 mm/sec. of scanning speed for 20 mm toobtain a laser-welded article.

Comparative Example 6

(6-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

The polycarbonate resin of catalog No. Panlite 1225Y available fromTEIJIN Limited and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour according to composition rates shownin Table 2. The obtained mixture was molded at 280° C. of temperature ofa cylinder and 80° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(6-B) Preparation of Laser-Absorptive Molded Workpiece

A laser-absorptive molded workpiece having the length of 80 mm, thewidth of 50 mm and the thickness of 1 mm was prepared by procedures assame as ones of (5-B) in Comparative Example 5.

(6-C) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(5-C) in Comparative Example 5.

Comparative Example 7

(7-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

The polycarbonate resin of catalog No. Panlite 1225Y available fromTEIJIN Limited and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour according to composition rates shownin Table 2. The obtained mixture was molded at 280° C. of temperature ofa cylinder and 80° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(7-B) Preparation of Laser-Absorptive Molded Workpiece

The polycarbonate resin of catalog No. Panlite 1225Y available fromTEIJIN Limited and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour according to composition rates shownin Table 2. The obtained mixture was molded at 280° C. of temperature ofa cylinder and 80° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-absorptive molded workpiece having the length of 80 mm, the widthof 50 mm and the thickness of 1 mm was prepared.

(7-C) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(5-C) in Comparative Example 5.

By using polypropylene resin, the laser-transmissible-absorptive moldedworkpiece and the laser-absorptive molded workpiece were manufacturedexperimentally, and then they were welded by the laser. Examples ofexperimentally manufacturing the laser-welded articles to which thepresent invention was applied are shown in Examples 11 to 13. Examplesof the laser-welded articles to which the present invention was notapplied are shown in Comparative Examples 8 to 10.

EXAMPLE 11

(11-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

499 g of polypropylene resin of catalog No. HG30U available from JapanPolychem Co., Ltd. and 1.0 g of nigrosine of catalog No. NUBIAN BLACKPC0850 available from Orient Chemical Industries, Ltd., and that NUBIANis the registered trademark were added in a tumbler made of stainlesssteel and were mixed with stirring for 1 hour. The obtained mixture wasmolded at 230° C. of temperature of a cylinder and 60° C. of temperatureof a metal mold with general procedures using the injection moldingmachine of catalog No. Si-50, which is available from Toyo Machinery &Metal Co., Ltd. Then a laser-transmissible-absorptive molded workpiecehaving the length of 80 mm, the width of 50 mm and the thickness of 1 mmwas prepared.

(11-b) Preparation of Laser-Absorptive Molded Workpiece

495 g of the polypropylene resin of catalog No. HG30U available fromJapan Polychem Co., Ltd. and 5.0 g of nigrosine of catalog No. NUBIANBLACK PC0850 available from Orient Chemical Industries, Ltd., and thatNUBIAN is the registered trademark were added in a tumbler made ofstainless steel and were mixed with stirring for 1 hour. The obtainedmixture was molded at 230° C. of temperature of a cylinder and 60° C. oftemperature of a metal mold with general procedures using the injectionmolding machine of catalog No. Si-50, which is available from ToyoMachinery & Metal Co., Ltd. Then a laser-absorptive molded workpiecehaving the length of 80 mm, the width of 50 mm and the thickness of 1 mmwas prepared.

(11-c) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 10 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 3 mm/sec. of scanning speed for 20 mm toobtain the laser-welded article.

EXAMPLE 12

(12-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

A laser-transmissible-absorptive molded workpiece having the length of80 mm, the width of 50 mm and the thickness of 1 mm was prepared byprocedures as same as ones of (11-a) in Example 1 1.

(12-b) Preparation of Laser-Absorptive Molded Workpiece

The polypropylene resin of catalog No. HG30U available from JapanPolychem Co., Ltd. and carbon black of catalog No. #32 available fromMitsubishi Chemical Corporation were added in a tumbler made ofstainless steel and were mixed with stirring for 1 hour according tocomposition rates shown in Table 3. The obtained mixture was molded at230° C. of temperature of a cylinder and 60° C. of temperature of ametal mold with general procedures using the injection molding machineof catalog No. Si-50, which is available from Toyo Machinery & MetalCo., Ltd. Then a laser-absorptive molded workpiece having the length of80 mm, the width of 50 mm and the thickness of 1 mm was prepared.

(1 2-c) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(11-c) in Example 11.

EXAMPLE 13

(13-a) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

499.5 g of the polypropylene resin of catalog No. HG30U available fromJapan Polychem Co., Ltd. and 0.5 g of nigrosine of catalog No. NUBIANBLACK PC0850 available from Orient Chemical Industries, Ltd., and thatNUBIAN is the registered trademark were added in a tumbler made ofstainless steel and were mixed with stirring for 1 hour. The obtainedmixture was molded at 230° C. of temperature of a cylinder and 60° C. oftemperature of a metal mold with general procedures using the injectionmolding machine of catalog No. Si-50, which is available from ToyoMachinery & Metal Co., Ltd. Then a laser-transmissible-absorptive moldedworkpiece having the length of 80 mm, the width of 50 mm and thethickness of 1 mm was prepared.

(13-b) Preparation of Laser-Absorptive Molded Workpiece

The polypropylene resin of catalog No. HG30U available from JapanPolychem Co., Ltd. and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark and carbon black of catalog No. #32 available fromMitsubishi Chemical Corporation were added in a tumbler made ofstainless steel and were mixed with stirring for 1 hour according tocomposition rates shown in Table 3. The obtained mixture was molded at230° C. of temperature of a cylinder and 60° C. of temperature of ametal mold with general procedures using the injection molding machineof catalog No. Si-50, which is available from Toyo Machinery & MetalCo., Ltd. Then a laser-absorptive molded workpiece having the length of80 mm, the width of 50 mm and the thickness of 1 mm was prepared.

(13-c) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(11-c) in Example 11.

Comparative Example 8

(8-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

500 g of the polypropylene resin of catalog No. HG30U available fromJapan Polychem Co., Ltd. was molded at 230° C. of temperature of acylinder and 60° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(8-B) Preparation of Laser-Absorptive Molded Workpiece

490 g of the polypropylene resin of catalog No. HG30U available fromJapan Polychem Co., Ltd. and 10 g of nigrosine of catalog No. NUBIANBLACK PC0850 available from Orient Chemical Industries, Ltd., and thatNUBIAN is the registered trademark were added in a tumbler made ofstainless steel and were mixed with stirring for 1 hour. The obtainedmixture was molded at 230° C. of temperature of a cylinder and 60° C. oftemperature of a metal mold with general procedures using the injectionmolding machine of catalog No. Si-50, which is available from ToyoMachinery & Metal Co., Ltd. Then a laser-absorptive molded workpiecehaving the length of 80 mm, the width of 50 mm and the thickness of 1 mmwas prepared.

(8-C) Manufacture of Laser-Welded Article

Then, the laser-transmissible-absorptive molded workpiece and thelaser-absorptive molded workpiece were piled and put together at oneportion thereof. The diode laser machine having 10 W of the output powerthat is available form Fine Device Co., Ltd. was used. The scanninglaser beam of the wavelength of 940 nm was continuously irradiated fromupper side of the laser-transmissible-absorptive molded workpiecetowards the put portion under 3 mm/sec, of scanning speed for 20 mm toobtain a laser-welded article.

Comparative Example 9

(9-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

The polypropylene resin of catalog No. HG30U available from JapanPolychem Co., Ltd. and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour according to composition rates shownin Table 3. The obtained mixture was molded at 230° C. of temperature ofa cylinder and 60° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(9-B) Preparation of Laser-Absorptive Molded Workpiece

A laser-absorptive molded workpiece having the length of 80 mm, thewidth of 50 mm and the thickness of 1 mm was prepared by procedures assame as ones of (8-B) in Comparative Example 8.

(9-C) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(8-C) in Comparative Example 8.

Comparative Example 10

(10-A) Preparation of Laser-Transmissible-Absorptive Molded Workpiece

The polypropylene resin of catalog No. HG30U available from JapanPolychem Co., Ltd. and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour according to composition rates shownin Table 3. The obtained mixture was molded at 230° C. of temperature ofa cylinder and 60° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-transmissible-absorptive molded workpiece having the length of 80mm, the width of 50 mm and the thickness of 1 mm was prepared.

(10-B) Preparation of Laser-Absorptive Molded Workpiece

The polypropylene resin of catalog No. HG30U available from JapanPolychem Co., Ltd. and nigrosine of catalog No. NUBIAN BLACK PC0850available from Orient Chemical Industries, Ltd. that NUBIAN is theregistered trademark were added in a tumbler made of stainless steel andwere mixed with stirring for 1 hour according to composition rates shownin Table 3. The obtained mixture was molded at 230° C. of temperature ofa cylinder and 60° C. of temperature of a metal mold with generalprocedures using the injection molding machine of catalog No. Si-50,which is available from Toyo Machinery & Metal Co., Ltd. Then alaser-absorptive molded workpiece having the length of 80 mm, the widthof 50 mm and the thickness of 1 mm was prepared.

(10-C) Manufacture of Laser-Welded Article

A laser-welded article was obtained by procedures as same as ones of(8-C) in Comparative Example 8.

Physical Evaluations

The workpieces and the laser-welded articles thereof of Examples andComparative Examples were evaluated by the following procedures forphysical evaluations.

(1) Calculation of an Absorbance (a) and an Absorption Coefficient(ε_(j))

The absorption coefficient was calculated as follows. By using aspectrophotometer of catalog No. V-570, which is available from JASCOCorporation, the transmissivity I_(T) of thelaser-transmissible-absorptive molded workpiece 1 with the thickness of1 mm (the thickness L₁=0.1(cm)) under the wavelength of 940 nm wasmeasured. Then the absorbance a₁ was calculated to by Lambert-Beer law,which is represented by the following numerical expression (IV)Absorbance a=−Log T=−Log {I _(T)/(I ₀ −I _(R))}  (IV)(In the expression (IV), I₀ is the incident light intensity, I_(T) isthe transmitted light intensity, I_(R) is the reflected lightintensity). Then, an analytical curve was prepared. The absorbance a₁ isrepresented by the following numerical expression (V).Absorbance a₁=ε₁C₁L₁  (V)

Therefore, the absorption coefficient ε₁ (1/cm) was calculated from theslope of the analytical curve. An absorbance a₂ was calculatedsimilarly. The absorbance a₂ is represented by the following numericalexpression.Absorbance a₂=ε₂C₂L₂  (V)(In the expression (VI), ε₂ (1/cm) is the absorption coefficient of thelaser-absorptive molded workpiece, C₂ (weight %) is the concentration ofthe laser absorbent included in the workpiece, L₂(cm) is the thicknessof the workpiece).(2) Tensile Strength Test

As regards the laser-welded articles obtained in Examples andComparative Examples, the tensile strength test using a tensile strengthtester of catalog No. AG-50kNE, which is available from ShimadzuCorporation, was executed as follows in order to determine the tensilestrength of the welding thereof. In accordance with Japanese IndustrialStandard K 7113-1995, the tensile strength of the welding was measuredby tensing the laser-welded article to both opposite dimensions oflengthwise, which pulls the welding position apart, under 10 mm/min. oftensile speed.

(3) Visual Observation of Appearance

The appearance of the laser-welded articles obtained in Examples andComparative Examples were judged by the visual observation to judge ifthe laser-welded articles were welded with hardly observing any burns ortraces of scanning the laser on the surface thereof.

The results of the physical evaluations of the laser-welded articles ofExamples and Comparative Examples are shown in Tables 1 to 3 together.TABLE 1 Examples of Laser-welded Article Comparative Using ExampleExample Polyamide-type Resin 1 2 3 4 5 6 1 2 3 4 *1 Composition Rate(Weight %) Polyamide6 99.98 99.93 99.93 99.9 0 99.93 100 0 99.4 99.93Polyamide66 0 0 0 0 99.96 0 0 100 0 0 Nigrosine 0.02 0.07 0.07 0.1 0.040.07 0 0 0.6 0.07 Property Thickness (mm) 1 1 1 1 1 1 1 1 1 1 Absorbance0.19 0.41 0.45 0.55 0.26 0.33 0.08 0.08 2.7 0.41 Transmissivity 60 37 3627 51 44 70 85 0.5 37 *ε 4.5 4.5 4.7 4.5 5.7 3.1 — — 4.5 4.5 *2Composition Rate (Weight %) Polyamide6 99.8 99.8 99.8 99.8 0 99.8 99.8 099.8 99.992 Polyamide66 0 0 0 0 99.7 0 0 99.8 0 0 Nigrosine 0 0 0 0 0.20 0 0 0 0.008 Carbon Black 0.2 0.2 0.2 0.2 0.1 0.2 0.2 0.2 0.2 0Property Thickness (mm) 1 1 1 1 1 1 1 1 1 1 Absorbance 2.9 2.9 2.9 2.92.2 2.9 2.9 2.9 3.1 0.04 Scanning Speed 2 1 1 1 4 1 2 4 2 1 (mm/sec.)Output Power of Laser (W) 10 10 10 10 10 10 10 10 10 10 Tensile Strength(N) 393.5 716.2 702.8 594.3 611.0 683.1 286.8 289.0 *No *No LaserWelding of *Ex *Ex *Ex *Ex *Ex *Ex *Ex *Ex — — Appearance*1: Laser-transmissible-absorptive Molded Workpiece*2: Laser-ansorptive Molded Workpiece*ε: Absorption Coefficient ε (× 10³)*Ex: Excellent*No: Not Welding

As it is evident with Table 1, the laser-welded articles using thepolyamide resin of Examples 1 to 6 are consisting of thelaser-transmissible-absorptive molded workpiece and the laser-absorptivemolded workpiece and are firmly welded respectively. And eachlaser-welded article had the excellent tensile strength.

On the other hand, the laser-welded articles of Comparative Examples 1and 2 include no nigrosine. Therefore, the molded workpieces wereallowed to be welded, but each laser-welded article had the insufficienttensile strength as compared with the laser-welded articles of Examples.

The laser-transmissible-absorptive molded workpiece of the laser-weldedarticle of Comparative Example 3 includes 0.6 weight % of nigrosine, andthe laser-absorptive molded workpiece of the laser-welded article ofComparative Example 4 includes merely 0.008 weight % of nigrosine.Therefore, the molded workpieces were not welded. TABLE 2 Examples ofLaser-welded Article Comparative Using Example Example PolycarbonateResin 7 8 9 10 5 6 7 *1 Composition Rate (Weight %) Polycarbonate 99.9899.9 99.86 99.86 100 99.4 99.9 Nigrosine 0.02 0.1 0.14 0.14 0 0.6 0.1Property Thickness 1 1 1 1 1 1 1 (mm) Absorbance 0.08 0.45 0.74 0.74 02.0 0.45 Transmissivity 78 33 18 18 91 1.2 33 *ε 3.3 3.3 3.3 3.3 — 3.33.3 *2 Composition Rate (Weight %) Polycarbonate 99 99 99 99.8 99 9999.992 Nigrosine 1 1 1 0 1 1 0.008 Carbon Black 0 0 0 0.2 0 0 0 PropertyThickness 1 1 1 1 1 1 1 (mm) Absorbance 3.7 3.7 3.7 5.8 3.7 3.7 0.02Scanning Speed 2 2 2 2 2 2 2 (mm/sec.) Output Power of Laser 8 8 8 8 8 88 (W) Tensile Strength (N) 232.2 330.1 385.3 678.1 201.2 *No *No LaserWelding of *Ex *Ex *Ex *Ex *Ex — — Appearance*1: Laser-Transmissible-absorptive Molded Workpiece*2: Laser-absorptive Molded Workpiece*ε: Ansorption Coefficient ε (× 10³)*Ex: Excellent*No: Not Welding

As it is evident with Table 2, the laser-welded articles using thepolycarbonate resin of Examples 7 to 10 are consisting of thelaser-transmissible-absorptive molded workpiece and the laser-absorptivemolded workpiece, and are firmly welded respectively. And eachlaser-welded article had the excellent tensile strength,

On the other hand, the laser-welded article of Comparative Example 5includes no nigrosine. Therefore, the molded workpieces were allowed tobe welded, but each laser-welded article had the insufficient tensilestrength as compared with the laser-welded articles of Examples.

The laser-transmissible-absorptive molded workpiece of the laser-weldedarticle of Comparative Example 6 includes 0.6 weight % of nigrosine, andthe laser-transmissible-absorptive molded workpiece of the laser-weldedarticle of Comparative Example 7 includes 0.1 weight % of nigrosine.Therefore, the molded workpieces were not welded. TABLE 3 Examples ofLaser-welded Article Comparative Using Example Example PolypropyleneResin 11 12 13 8 9 10 *1 Polypropylene 99.8 99.8 99.9 100 99.4 99.8Composition Nigrosine 0.2 0.2 0.1 0 0.6 0.2 Rate (Weight %) PropertyThickness (mm) 1 1 1 1 1 1 Absorbance 0.40 0.40 0.29 0.06 0.94 0.40Transmissivity 37 37 47 75 9 37 *ε 1.4 1.4 1.4 — 1.4 1.4 *2Polypropylene 99 99.87 99.6 98 98 99.992 Composition Nigrosine 1 0 0.3 22 0.008 Rate (Weight %) Carbon Black 0 0.13 0.1 0 0 0 Property Thickness(mm) 1 1 1 1 1 1 Absorbance 1.5 2.5 3.1 3.0 3.0 0.06 Scanning Speed 3 33 3 3 3 (mm/sec.) Output Power of Laser (W) 10 10 10 10 10 10 TensileStrength (N) 420.2 487.3 570.7 350.1 *No *No Laser Welding of *Ex *Ex*Ex *Ex — — Appearance*1: Laser-transmissible-absorptive Molded Workpiece*2: Laser-absorptive Molded Workpiece*ε: Absorption Coefficient ε (×10³)*Ex: Excellent*No: Not Welding

As it is evident with Table 3, the laser-welded articles using thepolypropylene resin of Examples 11 to 13 are consisting of thelaser-absorptive molded workpiece and the laser-transmissible-absorptivemolded workpiece, and are firmly welded respectively. And eachlaser-welded article had the excellent tensile strength.

On the other hand, the laser-welded article of Comparative Example 8includes no nigrosine. Therefore, the molded workpieces were allowed tobe welded, but each laser-welded article had the insufficient tensilestrength as compared with the laser-welded articles of Examples.

The laser-transmissible-absorptive molded workpiece of the laser-weldedarticle of Comparative Example 9 includes 0.6 weight % of nigrosine, andthe laser-absorptive molded workpiece of the laser-welded article ofComparative Example 10 includes merely 0.008 weight % of nigrosine.Therefore, the molded workpieces were not allowed to be welded.

INDUSTRIAL APPLICABILITY

The laser-welded article of the present invention is used for automotiveparts such as an instrument panel for automotive interior and asilencer: a resonater in engine room; medical apparatus such as amedical tubing used for an instillation of infusion; food pouch such asa spout pouch used for sealing fluid diet and beverage composition;electric or electronic parts; home electric appliances such as housingfor example.

1. A laser-welded article comprising: an integral construction of piledworkpieces, that are welded by exothermic through irradiating laser,comprises of a laser-transmissible-absorptive molded workpiece includinga thermoplastic resin and 0.001 to 0.3 weight % of colorant consistingof nigrosine which has an absorption coefficient: ε for a ray of 940 nmranging form 4000 to 7000 (ml/g·cm), that transmits laser partially andabsorbs laser partially, and a laser-absorptive molded workpieceincluding a thermoplastic resin and 0.1 to 5 weight % of diversecolorant comprising of nigrosine and/or carbon black, that absorbs thelaser.
 2. The laser-welded article according to claim 1, wherein thediverse colorant includes carbon black.
 3. The laser-welded articleaccording to claim 2, wherein the diverse colorant furthermore includesnigrosine.
 4. The laser-welded article according to claim 1, wherein thelaser-transmissible-absorptive molded workpiece satisfies the followingnumerical expression (I)0.07≦a₁=ε₁C₁L₁≦0.8  (I) (in the numerical expression (I), a₁ isabsorbance thereof, ε₁ (1/cm) is an absorption coefficient thereof, C₁(weight %) is concentration of the colorant therein, L₁ (cm) isthickness thereof).
 5. The laser-welded article according to claim 1,wherein the laser-absorptive molded workpiece satisfies the followingnumerical expression(II)1≦a₂=ε₂C₂L₂≦50  (II) (in the numerical expression(II), a₂ is absorbancethereof, ε₂ (1/cm) is an absorption coefficient thereof, C₂ (weight %)is concentration of the diverse colorant therein, L₂ (cm) is thicknessthereof).
 6. The laser-welded article according to claim 1, whereinnigrosine includes at least one selected from a group consisting ofcompounds represented by following chemical formulas (1) to (4).


7. The laser-welded article according to claim 1, wherein thelaser-transmissible-absorptive molded workpiece includes at least onethermoplastic resin selected from a group consisting of polyamide resin,polycarbonate resin, polyphenylene sulfide resin, polyester resin, andpolyolefin-type resin.
 8. The laser-welded article according to claim 7,wherein the laser-transmissible-absorptive molded workpiece includes thethermoplastic resin of polyamide resin and 0.01 to 0.2 weight % of thecolorant consisting of nigrosine.
 9. The laser-welded article accordingto claim 7, wherein the laser-transmissible-absorptive molded workpieceincludes the thermoplastic resin of polycarbonate resin and 0.01 to 0.2weight % of the colorant consisting of nigrosine.
 10. The laser-weldedarticle according to claim 1, wherein concentration of iron in nigrosineis 1% at maximum.
 11. The laser-welded article according to claim 1,wherein concentration of aniline in nigrosine is 1% at maximum.
 12. Thelaser-welded article according to claim 1, wherein thelaser-transmissible-absorptive molded workpiece and the laser-absorptivemolded workpiece have thickness ranging from 200 to 5000 microns. 13.The laser-welded article according to claim 1, wherein thelaser-transmissible-absorptive molded workpiece and the laser-absorptivemolded workpiece are films having thickness ranging from 200 to 1000microns.